Active energy ray curable composition, active energy ray curable ink, composition stored container, two dimensional or three dimensional image forming apparatus, image forming method, cured material, and processed product

ABSTRACT

An active energy ray curable composition includes a non-polymerizable resin; and polymerizable compounds comprising a mono-functional monomer having a single polymerizable unsaturated ethylene double bond, wherein the following relations are satisfied: ΔTg=|Tg p −Tg m }≧19 degrees C., where Tg p  represents a glass transition temperature of the non-polymerizable resin and Tg m  represents a glass transition temperature of a homopolymer of the mono-functional monomer, Tg H ≧10 degrees C., where Tg H  represents the higher of Tg p  and Tg m , and Tg L ≦40 degrees C., where Tg L  represents the lower of Tg p  and Tg m .

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application is based on and claims priority pursuant to 35U.S.C. §119(a) to Japanese Patent Application Nos. 2014-187589 and2015-139551, filed on Sep. 16, 2014 and Jul. 13, 2015, in the JapanPatent Office, the entire disclosures of which are hereby incorporatedby reference herein.

BACKGROUND

Technical Field

The present invention relates to an active energy ray curablecomposition, an active energy ray curable ink, a composition storedcontainer, a two dimensional or three dimensional image formingapparatus, an image forming method, a cured material, and a processedproduct

Background Art

Photopolymerizable inks are conventionally used or supplied for offset,silk screen, top coating agents, etc. and become popular due to its costreduction by simplifying drying processes and advantages such as lessvolatile amounts of solvents, which is good for protection of theenvironment.

Of these, aqueous-based and solvent-based inkjet inks are most commonlyand selectively used to particular applications. However, aqueous-basedand solvent-based inkjet inks involve drawbacks such that the variety ofsubstrates (materials to which ink is applied, recording medium, etc.)for industrial use is limited, such inks have relatively poor waterresistance and large drying energy, and the ink components are attachedto a head as they dry. Therefore, replacement of the aqueous-based andsolvent-based inkjet inks with photopolymerizable inks having relativelylow volatility is researched and studied.

With regard to the photopolymerizable inkjet ink, after thephotopolymerizable inkjet ink is applied to a substrate, post-processingto the recorded matter is increasingly required.

Cured materials of typical photopolymerizable inkjet inks are hard butbrittle in most cases. Therefore, mono-functional monomers are added tothe ink to secure extensibility required for such processing. However,simply adding such monomers is not sufficient to obtain a cured materialhaving a desired hardness. In addition, if a polymerizablemulti-functional monomer is used to maintain hardness of a curedmaterial, extensibility deteriorates. That is, there is trade-offbetween hardness and extensibility.

In addition, in attempts to obtain a hard cured material, a mercurylight or an irradiator to emit a low energy ray such as an ultravioletlaser beam as a device is used to cure a photopolymerizable inkjet ink.However, these are also not sufficient to improve hardness.

SUMMARY

According to the present invention, provided is an improved activeenergy ray curable composition including a non-polymerizable resin andpolymerizable compounds including a mono-functional monomer having asingle polymerizable unsaturated ethylene double bond, wherein thefollowing relations are satisfied:ΔTg=|Tg _(p) −Tg _(m)|≧19 degrees C.where Tg_(p) represents the glass transition temperature of thenon-polymerizable resin and Tg_(m) represents the glass transitiontemperature of a homopolymer of the mono-functional monomer,Tg_(H)≧10 degrees C.,where Tg_(H) represents the higher of Tg_(p) and Tg_(m), andTg_(L)≦40 degrees C.,where Tg_(L) represents the lower of Tg_(p) and Tg_(m).

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

Various other objects, features and attendant advantages of the presentinvention will be more fully appreciated as the same become betterunderstood from the detailed description when considered in connectionwith the accompanying drawings, in which like reference charactersdesignate like corresponding parts throughout and wherein

FIG. 1 is a schematic diagram illustrating an example of a twodimensional image forming apparatus according to an embodiment of thepresent invention;

FIG. 2 is a schematic diagram illustrating an example of the threedimensional image forming apparatus according to an embodiment of thepresent invention; and

FIGS. 3A, 3B, 3C, and 3D are schematic diagrams illustrating anotherexample of the three dimensional image forming apparatus according to anembodiment of the present invention.

DETAILED DESCRIPTION

The present invention provides an active energy ray curable compositionby which a cured material is obtained striking a balance between highhardness and extensibility while maintaining bending property.

The present disclosure will be described below in detail with referenceto several embodiments and accompanying drawings.

The active energy ray curable composition of the present disclosureincludes a non-polymerizable resin and polymerizable compounds includinga mono-functional monomer having a polymerizable unsaturated ethylenedouble bond, wherein the following relations are satisfied:ΔTg=|Tg _(p) −Tg _(m)|≧19 degrees C.,where Tg_(p) represents the glass transition temperature of thenon-polymerizable resin and Tg_(m) represents the glass transitiontemperature of the homopolymer of the mono-functional monomer,Tg_(H)≧10 degrees C.,where Tg_(H) represents the higher of Tg_(p) and Tg_(m), andTg_(L)≦40 degrees C.,where Tg_(L) represents the lower of Tg_(p) and Tg_(m).

In the present disclosure, the mono-functional monomer represents amonomer having a single polymerizable unsaturated ethylene double bond.

Specific examples thereof include, but are not limited to, the followingmonomers: phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isoboronylacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutylacrylate, t-butyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate,methoxytriethyleneglycol acrylate, 2-ethoxylethyl acrylate,3-methoxybutyl acrylate, ethoxyethyl acrylate, buthoxyethyl acrylate,ethoxydiethyleneglycol acrylate, ethoxydiethyleneglycol acrylate,methoxydiethylethyl acrylate, ethyldiglycol acrylate, cyclic trimethylpropane formal monoacrylate, imide acrylate, isoamyl acrylate,ethoxified succinic acid acrylate, trifluoroethyl acrylate,omega-carboxylpolycaprolactone monoacrylate, N-vinylformamide,cyclohexylacrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate,tribromophenyl acrylate, ethoxified tribromophenyl acrylate,2-phenoxyethyl acrylate, acryloyl morpholine, phenoxydiethylene glycolacrylate, vinylcaprolactam, vinylpyrrolidone, 2-hydroxy-3-phenoxypropylacrylate, 1,4-cyclohexane dimethanol monoacrylate, 2-(2-ethoxy)ethylacrylate, stearyl acrylate, diethylene glycolmonobutylether acrylate,lauryl acrylate, isodecyl acrylate, 3,3-5-trimethylcyclohexane acrylate,isooctyl acrylate, octyl/decyl acrylate, tridecyl acrylate, caprolactoneacryl ate, ethoxified (4) nonylphenol acrylate, methoxypolyethyleneglycol (350) monoacrylate, and methoxypolyethylene glycol (550)monoacrylate. These compounds are selectively used depending on thedifference between Tg_(m) of the homopolymer and the Tg_(p) of thenon-polymerizable resin.

The mono-functional monomer having a single polymerizable unsaturatedethylene double bond accounts for 50 percent by mass to 100 percent bymass of the total content of the polymerizable compounds in the activeenergy ray curable composition. It is more preferably from 60 percent bymass to 100% by mass and more preferably from 80% by mass to 100% bymass.

In the present disclosure, non-polymerizable resin having nopolymerizable unsaturated ethylene double bond is used as the resin.Examples thereof are the following: Acrylic-based resin, epoxy-basedresins, ketone-based resins, nitrocellulose-based resins, phenoxy-basedresins, polyester-based resins, polyurethane-based resins, and polyvinylchloride(PVC)-based resins, and polymers selected from mixtures thereof.

Specific examples of the acrylic-based resins include, but are notlimited to, JONCRYL® (manufactured by BASF Japan), S-LEC P (manufacturedby SEKISUI CHEMICAL CO., LTD.), and Elvacite 4026 and Elvacite 2028(manufactured by Lucite International, INC). Specific examples of thepolyester-based resins include, but are not limited to, ELITEL®(manufactured by UNITIKA LTD.) and VYLON (manufactured by TOYOBO CO.,LTD.), Polyester MSP-640 (manufactured by Nippon Synthetic ChemicalIndustry Co., Ltd.). Specific examples of the polyurethane-based resinsinclude, but are not limited to, VYLON UR (manufactured by TOYOBO CO.,LTD.), NT-HI LAMIC (manufactured by Dainichiseika Color and ChemicalsMfg. Co., LTD.), CRISVON (manufactured by DIC Corporation), andNIPPOLLAN (manufactured by NIPPON POLYURETHANE INDUSTRY CO. LTD.).Specific examples of the PVC-based resins include, but are not limitedto, SOLBIN and Vinyblan (manufactured by Nisshin Chemical Co., Ltd.),Sara Latex (manufactured by Asahi Kasei Chemicals Corporation),SUMIELITE™ (manufactured by Sumitomo Chemical Co., Ltd.), Sekisui PVC(manufactured by SEKISUI CHEMICAL CO., LTD.), and UCAR (manufactured byThe Dow Chemical Company). Specific examples of the ketone-based resinsinclude, but are not limited to, Hilac (manufactured by Hitachi ChemicalCo., Ltd.) and SK (manufactured by Degusa), Specific examples of theepoxy-based resins include, but are not limited to, EPPN-201(manufactured by Nippon Kayaku Co., Ltd.) and HP-7200 (manufactured byDIC Corporation). Specific examples of the nitrocellulose-based resinsinclude, but are not limited to, HIG, LIG, SL, and VX (manufactured byAsahi Kasei Chemicals Corporation), nitrocellulose for industrial use RSand SS (manufactured by Daicel Corporation). Specific examples of thephenoxy-based resins include, but are not limited to, YP-50 and YP-50S(manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.).

The weight average molecular weight Mw of the non-polymerizable resin ispreferably from 1,500 to 70,000. The molecular weight is preferably2,000 or more and more preferably 3,000 or more, preferably 30,000 orless, and more preferably 20,000 or less. The weight average molecularweight Mw can be measured by known technologies, for example, gelpermeation chromatography (GPC).

The content of the non-polymerizable resin preferably accounts for 0.1percent by mass to 5 percent by mass and more preferably 0.1 percent bymass to 3 percent by mass of the total content of the polymerizablecompounds (100 percent by mass).

In general, as the molecular weight or the content of a resin increases,the viscosity thereof tends to increase. For this reason, the contentthat can be added to a composition decreases. Therefore, the balancebetween the content of a resin added to the composition and themolecular weight of the resin is appropriately determined consideringjetting (discharging) characteristics.

In the present disclosure, the following relation is satisfied:ΔTg=|Tg _(p) −Tg _(m)|≧19 degrees C.,where Tg_(p) represents a glass transition temperature of thenon-polymerizable resin and Tg_(m) represents a glass transitiontemperature of the homopolymer of the mono-functional monomer having apolymerizable unsaturated ethylene double bond. This means, both amaterial having a high Tg and a material having a low Tg are used tostrike a balance between hardness and flexibility of an obtained curedmaterial.

In addition, in the present disclosure, the following relations aresatisfied:Tg_(H)≧10 degrees C.,where Tg_(H) represents the higher of Tg_(p) and Tg_(m), andTg_(L)≦40 degrees C.,where Tg_(L) represents the lower of Tg_(p) and Tg_(m).

When the Tg_(H) is lower than 10 degrees C., an obtained cured materialis soft (low hardness). For this reason, for example, the material canbe easily scratched by nail when a film is formed thereon.

When the Tg_(L) surpasses 40 degrees C., shock resistance and bendingproperty of an obtained cured material are inferior and not suitable forpractical use.

Tg_(H) is preferably not lower than 14 degrees C. and more preferablynot lower than 20 degrees C. Tg_(L) is preferably not higher than 20degrees C., more preferably not higher than 10 degrees C., andfurthermore preferably not higher than 0 degrees C.

Moreover, the active energy ray curable composition furthermorepreferably satisfies the following relations: Tg_(p)≧10 degrees C. andTg_(m)≦40 degrees. More preferably, Tg_(p) is not lower than 10 degreesC. and Tg_(m) is not higher than 20 degrees C.

The glass transition temperature Tg_(p) of the non-polymerizable resinis easily controlled when designing the resin. Also, sincemono-functional monomers having a high glass transition temperatureTg_(m) are few, monomers having a Tg_(p) higher than Tg_(m) have widerranges of selections, thereby increasing the freedom of formulation.

When two or more kinds of the non-polymerizable resins and two or morekinds of the monofunctional monomers having a polymerizable unsaturatedethylene double bond are used, the glass transition temperatures Tg_(p)and Tg_(m) are calculated according to the mass ratio of each resin tothe total content of the non-polymerizable resins or the mass ratio ofeach mono-functional monomer to the total content of the monofunctionalmonomers.

For example, when a resin 1 and a resin 2 are used as thenon-polymerizable resin, the glass transition temperature Tg_(p) of thenon-polymerizable resins is calculated by the following relation.Tg _(p)=(Tg _(p1)×content of resin 1/total content of resins)+(Tg_(p2)×content of resin 2/total content of resins),where Tg_(p1) represents the glass transition temperature of the resin 1and Tg_(p2) represents the glass transition temperature of the resin 2.

For example, when a mono-functional monomer 1 and a mono-functionalmonomer 2 are used as the mono-functional monomer, the glass transitiontemperature Tg_(m) of the homopolymer of the mono-functional monomer iscalculated by the following relation.Tg _(m)=(Tg _(m1)×content of mono-functional monomer 1/total content ofmono-functional monomers)+(Tg _(m2)×content of mono-functional monomer2/total content of mono-functional monomers),where Tg_(m1) represents the glass transition temperature of homopolymerof the mono-functional monomer 1 and Tg_(p2) represents the glasstransition temperature of the homopolymer of the mono-functional monomer2.

The active energy ray curable composition of the present disclosureoptionally contains a multi-functional monomer having two or morepolymerizable unsaturated ethylene double bonds in an amount of 15% bymass or less to the total amount of the polymerizable compound.

Specific examples of the multi-functional monomer include, but are notlimited to the following: hexadiol diacrylate, trimethylol propanetriacrylate, pentaerythritol triacrylate, polyethyleneglycol diacrylate,dipropyleneglycol diacrylate, tripropyleneglycol triacrylate,neopentylglycol diacrylate, bispentaerythritol hexaacrylate, ethyleneglycol diacrylate, diethylene glycol diacrylate, 1,6-hexane dioldiacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycoldiacrylate, 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate,tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl 1,3-propane dioldiacrylate, hydroxy pivalic acid neopentyl glycol diacrylate,1,3-butylene glycol di(meth)acrylate, trimethylol propane triacrylate,hydroxy pivalic acid trimethylol propane triacrylate, ethoxylatedphosphoric acid triacrylate, ethoxylated tripropylene glycol diacrylate,neopentyl glycol-modified trimethylol propane diacrylate, stearylacid-modified pentaerythritol diacrylate, pentaerythritol triacrylate,tetramethylol propane triacrylate, tetramethylol methane triacrylate,pentaerithritol tetraacrylate, caprolacone-modified trimethylo propanetriacrylate, propoxylate glyceryl triacrylate, tetramethylolmethanetetraacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate,dipentaerythritol hexaaxrylate, caprolacotone-modified dipentaerythritolhexaacrylate, dipentaerythritol hydroxy pentaacrylate, neopentylglycololigoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediololigoacrylate, trimethylolpropane oligoacrylate, pentaerythritololigoacrylate, ethoxylated neopentylglycol di(meth)acrylate,propoxylated neopentylglycol di(meth)acrylate, tripropylene glycoldi(meth)acrylate, ethoxylated trimethylol propanetriacrylate, andpropoxylated trimethylol propane triacrylate.

These multi-functional monomers can be used alone or in combination.

Good curability is obtained by mixing with the multi-functionalmonomers.

Furthermore, when a high level of extensible processibility is required,bifunctional monomers are preferably used as the multi-functionalmonomer. Using only bifunctional monomers as the multi-functionalmonomer is more preferable.

When the mixing amount of the multi-functional monomer is 15 percent bymass or less to the total amount of the polymerizable compounds, morepreferable cured film is formed. It is preferably 10 percent by mass orless and more preferably 5% by mass or less. When the content of themulti-functional monomer is 15 percent by mass or less, more preferableextensibility is obtained.

The active energy ray curable composition of the present disclosure maycontain oligomers having a polymerizable unsaturated ethylene doublebond(s) in an amount of 10% by mass or less to the total amount of thepolymerizable compound.

The oligomer for use in the present disclosure includes a polymerizableunsaturated ethylene double bond and specific examples thereof include,but are not limited to, aromatic urethane oligomers, aliphatic urethaneoligomers, epoxyacrylate oligomers, polyesteracrylate oligomers, andother special oligomers.

Specific examples thereof available on market include, but are notlimited to the following: UV-2000B, UV-2750B, UV-3000B, UV-3010B,UV-3200B, UV-3300B, UV-3700B, UV-6640B, UV-8630B, UV-7000B, UV-7610B,UV-1700B, UV-7630B,UV-6300B, UV-6640B, UV-7550B, UV-7600B, UV-7605B,UV-7610B, UV-7630B, UV-7640B, UV-7650B, UT-5449, and UT-5454 (allmanufactured by The Nippon Synthetic Chemical Industry Co., Ltd., CN902,CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E75, CN961H81,CN962, CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN963J85, CN964,CN965, CN965A80, CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN968,CN969, CN970, CN970A60, CN970E60, CN971, CN971A80, CN971J75, CN972,CN973, CN973A80, CN973H85, CN973J75, CN975, CN977, CN977C70, CN978,CN980, CN981, CN981A75, CN981B88, CN982, CN982A75, CN982B88, CN982E75,CN983, CN984, CN985, CN985B88, CN986, CN989, CN991, CN992, CN994, CN996,CN997, CN999, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008,CN9009, CN9010, CN9011, CN9013, CN9018, CN9019, CN9024, CN9025, CN9026,CN9028, CN9029, CN9030, CN9060, CN9165, CN9167, CN9178, CN9290, CN9782,CN9783, CN9788, and CN9893 (all manufactured by Sartomer Company), andEBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, KRM8200, EBECRYL5129,EBECRYL8210, EBECRYL8301, EBECRYL8804, EBECRYL8807, EBECRYL9260,KRM7735, KRM8296, KRM8452, EBECRYL4858, EBECRYL8402, EBECRYL9270,EBECRYL8311, and EBECRYL8701 (all manufactured by Daicel-Cytec CompanyLtd.). These can be used alone or in combination.

When the mixing amount of the oligomer is 10 percent by mass or less tothe total amount of the polymerizable compounds, extensibility andcurability are improved, thereby to form more preferable cured film. Itis preferably 8 percent by mass or less. It is more preferably 5% bymass or less. When the content of the oligomer is 10 percent by mass orless, more preferable extensibility is obtained.

The oligomers preferably have two to five unsaturated carbon-carbonbonds and most preferably two bonds. When the oligomer has two bonds,good extensibility is obtained.

Polymerization initiators are preferably used for the curablecomposition of the present disclosure. The polymerization initiatorproduces active species such as a radical or a cation upon applicationof energy of an active energy ray and initiates polymerization of apolymerizable compound (monomer or oligomer). Of these, radicalpolymerization initiators are preferable.

A polymerization initiator that is inexpensive and generates no strongacid can be used for the active energy ray curable composition of thepresent disclosure. Therefore, it is possible to produce the curablecomposition at low cost and also it is easy to choose members for aprinter. When using an extremely high energy light source such aselectron beams, a ray, β ray, γ ray, or X ray, polymerization reactionproceeds without a polymerization initiator. This is a conventionallyknown matter and is not described in the present disclosure in detail.

In addition, the content of the polymerization initiator is notparticularly limited but it is preferably from one percent by mass to 20percent by mass and more preferably from 5 percent by mass to 15 percentby mass to the total content of the polymerizable compounds.

The radical polymerization initiator include, but are not limited to, aself-cleaving type and a hydrogen-abstraction type. Specific examples ofthe self-cleaving type include, but are not limited to,2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy cyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl propane-1-one,1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one,2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-1-propane-1-one,oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone, phenylglyoxyic acid methyl ester,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino propane-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl-phenyl)butane-1-one,bis(2,4,6-trimethylbenzoyl)-phenyl phosphineoxide,bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentyl phosphine oxide,2,4,6-trimethyl benzoyl-phosphine oxide, 1,2-octanedione-[4-(phenylthio)-2-(o-benzoyloxime],ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(o-acetyloxime)]}, and[4-(methylphenylthio)phenyl]phenyl methanone.

Specific examples of the hydrogen-abstraction type include, but are notlimited to, benzophenone-based compounds such as benzophenone,methylbenzophenone, methyl-2-benzoylbenzoate,4-benzoyl-4′-methyldiphenyl sulfide and phenylbenzophenone; andthioxanthone-based compounds such as 2,4-diethylthioxanthone,2-chlorothioxanthone, isopropylthioxanthone, and1-chloro-4-propylthioxanthone.

Amine compounds can be used in combination as an polymerizationaccelerator.

Specific examples thereof include, but are not limited to,p-dimethylamino ethylbenzoate, p-dimethylamino-2-ethylhexylbenzoate,p-dimethylamino methylbenzoate, 2-dimethylaminoethyl benzoate, andp-dimethyl butoxyethylaminobenzoate.

With regard to the monomer component of the active energy ray curablecomposition of the present disclosure, the compounds thereof aredetermined by utilizing gaschromatography mass spectrometry (GC/MS) andthe Tg of the homopolymer thereof can be measured by the differentialscanning calorimetry (DSC). With regard to the polymer component, an inkis extracted by a poor solvent of the polymer, just the polymercomposition is extracted and the Tg of the polymer can be similarlymeasured by DSC. Therefore, the active energy ray curable composition ofthe present disclosure can be identified.

Active Energy Ray

Active energy rays for use in curing an active energy ray curablecomposition of the present disclosure are not particularly limited, forexample, they are preferred when they can impart energy to conductpolymerization reaction of polymerizable components in the curablecomposition.

Specific examples thereof include, but are not limited to, electronbeams, αray, β ray, γ ray, and X ray, in addition to ultraviolet rays.Preferably, in another embodiment, a particularly high energy lightsource obviates the need for a polymerization initiator to proceedreaction. In addition, in the case of irradiation with ultraviolet ray,mercury-free is strongly preferred in terms of protection ofenvironment. Therefore, replacement with GaN-based ultravioletlight-emitting devices is preferred from industrial and environmentalpoint of view. Furthermore, ultraviolet light-emitting diode (UV-LED)and ultraviolet laser diode (UV-LD) are preferable. Small size, longworking life, high efficiency, and high cost performance make suchirradiation sources desirable.

Colorant

The active energy ray curable composition of the present disclosureoptionally contains a colorant. As the colorant, although depending onthe objectives and requisites of the composition of the presentdisclosure, various pigments and dyes are suitable, which impart black,white, magenta, cyan, yellow, green, orange, and gloss color such asgold and silver. The content of the colorant is not particularly limitedand may be determined considering the desired color density anddispersibility of the colorant in the curable composition, etc. It ispreferred that the content of the colorant accounts for 0.1 percent bymass to 20 percent by mass of the total content (100 percent by mass) ofthe composition. Incidentally, the active energy ray curable compositionof the present disclosure does not necessarily contain a colorant butcan be clear and colorless. If no colorant is present in thecomposition, the composition is suitable as an overcoat layer forprotecting an image

The pigment can be inorganic or organic and a combination thereof.

Specific examples of the inorganic pigments include, but are not limitedto, carbon blacks (C.I. Pigment Black 7) such as furnace black, lampblack, acetylene black, and channel black, iron oxides, and titaniumoxides.

Specific examples of the organic pigments include, but are not limitedto, azo pigments such as insoluble azo pigments, condensed azo pigments,azo lakes, chelate azo pigments, etc.), polycyclic pigments such asphthalocyanine pigments, perylene pigments, perinone pigments,anthraquinone pigments, quinacridone pigments, dioxane pigments,thioindigo pigments, isoindolinone pigments, and quinofuranone pigments,nitro pigments, nitroso pigments, aniline black, and daylightfluorescent pigments.

In addition, a dispersant is optionally added to enhance thedispersibility of a pigment. The dispersant has no particular limit andcan be, for example, polymer dispersants conventionally used to preparea pigment dispersion material.

The dyes is not particularly limited and include, for example, acidicdyes, direct dyes, reactive dyes, basic dyes, and combinations thereof.

Organic Solvent

The active energy ray curable composition of the present disclosureoptionally contains an organic solvent although it is preferable tospare it. The curable composition free of an organic solvent, inparticular volatile organic compound (VOC) is preferable because itenhances safety at where the composition is handled and makes itpossible to prevent pollution of the environment. Incidentally, theorganic solvent represents a conventional non-reactive organic solvent,for example, ether, ketone, xylene, ethylacetate, cyclohexanone, andtoluene, which is clearly distinguished from reactive monomers.Furthermore, “free of” an organic solvent means that no organic solventis substantially contained. The content thereof is preferably less than0.1 percent by mass.

Preparation of Active Energy Ray Curable Composition

The active energy ray curable composition of the present disclosure canbe prepared by using the components described above. The preparationdevices and conditions are not particularly limited.

For example, the curable composition can be prepared by charging apolymerizable monomer, a pigment, a dispersant, etc., into a dispersingmachine such as a ball mill, kitty mill, a disk mill, a pin mill, and aDYNO-MILL to prepare a pigment liquid dispersion followed by mixing witha polymerizable monomer, an initiator, a polymerization inhibitor, and asurfactant.

Viscosity

The viscosity of the active energy ray curable composition of thepresent disclosure has no particular limit because it can be adjusteddepending on the purpose and application devices. For example, if adischarging device that discharges the composition from nozzles isemployed, the viscosity thereof is preferably in the range of from 3mPa·s to 40 mPa·s, more preferably from 5 mPa·s to 15 mPa·s, andparticularly preferably from 6 mPa·s to 12 mPa·s in the temperaturerange of from 20 degrees C. to 65 degrees C., preferably at 25 degreesC. In addition, it is particularly preferable to satisfy this viscosityrange by a composition free of the organic solvent mentioned above. Theviscosity can be measured with a cone-and-plate rotary viscometerVISCOMETER TVE-22L manufactured by Toki Sangyo Co., using a cone rotor(1°34′×R24), at a rotation speed of 50 rpm, with the temperature ofhemathermal circulating water appropriately set in a range of from 20degrees C. to 65 degrees C. VISCOMATE VM-150III can be used for thetemperature adjustment of the circulating water.

Application Field

The application field of the active energy ray curable composition ofthe present disclosure is not particularly limited. It can be applied toany field where the active energy ray curable composition is used. Forexample, the curable composition is selected to a particular applicationand used for a resin for processing, a paint, an adhesive, an insulant,a release agent, a coating material, a sealing material, variousresists, and various optical materials.

Furthermore, the active energy ray curable composition of the presentdisclosure can be used as an ink to form two-dimensional texts, images,and designed coating film on various substrates and in addition as asolid object forming material to form a three-dimensional solid object(additive manufacturing). This material for a three-dimensional objectcan be used as a binder for powder particles for use in powder additivemanufacturing to form a solid object by repeating curing and laminatingpowder layers. Also, it can be used as a three-dimensional objectconstituting material (model material) or supporting member (supportingmaterial) for use in additive manufacturing as illustrated in FIG. 2,FIG. 3A, FIG. 3B, FIG. 3C, and 3D. FIG. 2 is a diagram illustrating amethod of additive manufacturing to sequentially form layers of theactive energy ray curable composition of the present disclosure one ontop of the other by repeating discharging, curing, and laminating thecurable composition. FIGS. 3A to 3D are diagrams illustrating a methodof additive manufacturing to sequentially form cured layers 6 one on topof the other having respective predetermined forms on a movable stage 3by irradiating with the active energy ray 4 a storing pool (storingpart) 1 of the active energy ray curable composition 5 of the presentdisclosure.

An apparatus configured to fabricate a three-dimensional object by theactive energy ray curable composition of the present disclosure can be aknown apparatus with no particular limit. For example, an apparatus issuitable which includes an accommodating device, a supplying device, anda discharging device of the curable composition, and an active energyray irradiator.

In addition, the present disclosure includes cured materials obtained bycuring the active energy ray curable composition and structures formedof the cured materials and a substrate on which the cured materials areformed. The structure can be processed to obtain a molded product. Theprocessed product is fabricated by, for example, forming processing suchas heating drawing and punching of cured materials and structures havinga sheet-like form or film-like form.

These are suitably used for, for example, gauges or operation panels ofvehicles, office machines, electric and electronic machines, andcameras, which requires processing the surface after decorating.

The substrate is not particularly limited. It can suitably be selectedto a particular application. Specific examples thereof include, but arenot limited to, paper, fiber, fabrics, leather, metal, plastic, glass,wood, ceramic, or composite materials thereof. Of these, plasticsubstrates are preferred in terms of processibility.

Composition Stored Container

The composition stored container of the present disclosure contains theactive energy ray curable composition and is suitable for theapplication fields as described above. For example, if the active energyray curable composition of the present disclosure is for ink, acontainer accommodating the ink can be used as in a form of an inkcartridge or an ink bottle. Therefore, users can avoid direct contactwith the ink during operations such as transfer or replacement of theink, so that fingers and clothes are prevented from contamination.Furthermore, inclusion of foreign matters such as dust in the ink can beprevented. In addition, the container can be of any size, any form, andany material. For example, the container can be designed for anyparticular purpose and usage. It is preferable to use a light blockingmaterial to block the light or cover a container with a light blockingsheet, etc.

Image Forming Method and Image Forming Apparatus

The image forming method of the present disclosure includes at least anirradiating step of irradiating the curable composition of the presentdisclosure with an active energy ray to cure the curable composition.The image forming apparatus of the present disclosure includes at leastan irradiator to irradiate the curable composition of the presentdisclosure with an active energy ray and a storing part containing theactive energy ray curable composition of the present disclosure. Thestoring part may include the container mentioned above. Furthermore, themethod and the apparatus optionally include a discharging step and adischarging device to discharge the active energy ray curablecomposition, respectively. The method of discharging the curablecomposition is not particularly limited, and examples thereof include acontinuous spraying method and an on-demand method. The on-demand methodincludes a piezo method, a thermal method, an electrostatic method, etc.

FIG. 1 is a diagram illustrating an image forming apparatus equippedwith an inkjet discharging device. Printing units 23 a, 23 b, 23 c, and23 d having ink cartridges and discharging heads for yellow, magenta,cyan, and black active energy ray curable inks, respectively dischargethe inks onto a recording medium 22 fed from a supplying roller 21.Thereafter, light sources 24 a, 24 b, 24 c, and 24 d emit active energyrays to cure the inks to form a color image. Thereafter, the recordingmedium 22 is transferred (conveyed) to a processing unit 25 and aprinted matter reeling roll 26. Each of the printing unit 23 a, 23 b, 23c and 23 d optionally has a heating mechanism to liquidize the ink atthe ink discharging portion. Moreover, in another embodiment of thepresent disclosure, a mechanism may optionally be included to cool downthe recording medium to around room temperature in a contact ornon-contact manner. In addition, the inkjet recording method can be anyof a serial method of discharging an ink onto a recording medium that isintermittently moving to the width of a discharging head by moving thehead or a line method of discharging an ink onto a recording medium thatis moving continuously from a discharging head held at a fixed position.

The recording medium 22 is not particularly limited. Specific examplesthereof include, but are not limited to, paper, film, metal, or complexmaterials thereof. The recording medium 22 takes a sheet-like form butis not limited thereto. The image forming apparatus may have a one-sideprinting configuration or a two-side printing configuration.

Optionally, multiple colors can be printed with no or faint activeenergy ray from the light sources 24 a, 24 b, and 24 c followed byirradiation of the active energy ray from the light source 24 d. As aresult, energy and cost can be saved.

The recorded matter on which images are printed with the ink of thepresent disclosure includes articles having images or texts on a plainsurface of conventional paper, resin film, etc. a rough surface, or asurface made of various materials such as metal or ceramic. In addition,by laminating layers of images in part or the entire of a recordingmedium, a partially stereoscopic image (formed of two dimensional partand three-dimensional part) and a three dimensional objects can befabricated.

FIG. 2 is a schematic diagram illustrating another example of the imageforming apparatus (apparatus to fabricate a 3D object) of the presentdisclosure. An image forming apparatus 39 illustrated in FIG. 2sequentially forms layers one on top of the other using a head unithaving inkjet heads arranged movable in the directions indicated by thearrows A and B while discharging a first active energy ray curablecomposition from a discharging head unit 30 for additive manufacturingand a second active energy ray curable composition composed of differentingredients from the first active energy ray curable composition fromdischarging head units 31 and 32 for support and curing thesecompositions by ultraviolet irradiators 33 and 34 adjacent to thedischarging head units 31 and 32. To be more specific, for example,after the discharging head units 31 and 32 for support discharge thesecond active energy ray curable composition onto a substrate 37 foradditive manufacturing and the second active energy ray curablecomposition is solidified by irradiation of an active energy ray to forma first substrate layer having a hollow space for fabrication, thedischarging head unit 30 for additive manufacturing discharges the firstactive energy ray curable composition onto the hollow space followed byirradiation of an active energy ray for solidification, thereby to forma first additive manufacturing layer. This step is repeated multipletimes lowering the stage 38 movable in the vertical direction tolaminate the support layer and the additive manufacturing layer tofabricate a solid object 35. Thereafter, an additive manufacturingsupport 36 is removed, if desired. Although only a single discharginghead unit 30 for additive manufacturing is provided to the image formingapparatus illustrated in FIG. 2, it can have two or more discharginghead units 30.

The present invention relates to the active energy ray curablecomposition and include the following embodiments 2 to 14.

-   1. An active energy ray curable composition including a    non-polymerizable resin and a mono-functional functional monomer    having a polymerizable unsaturated ethylene double bond, wherein the    following relations are satisfied:    ΔTg=|Tg _(p) −Tg _(m)|≧19 degrees C.,    where Tg_(p) represents a glass transition temperature of the    non-polymerizable resin and Tg_(m) represents a glass transition    temperature of a homopolymer of the mono-functional monomer,    Tg_(H)≧10 degrees C.,    where Tg_(H) represents the higher of Tg_(p) and Tg_(m), and    Tg_(L)≦40 degrees C.,    where Tg_(L) represents the lower of Tg_(p) and Tg_(m).-   2. The active energy ray curable composition according to 1    mentioned above, wherein the following relations are furthermore    satisfied:    Tg_(p)≧10 degrees C. and Tg_(m)≦40 degrees C.-   3. The active energy ray curable composition according to 1 or 2    mentioned above, wherein the following relations are furthermore    satisfied:    Tg_(p)≧10 degrees C. and Tg_(m)≦20 degrees C.-   4. The active energy ray curable composition according to any one of    1 to 3 mentioned above, wherein the non-polymerizable resin is an    acylic-based resin, an epoxy-based resin, a ketone-based resin, a    nitrocellulose-based resin, a phenoxy-based resin, a polyester-based    resin, a polyurethane-based resin, a polyvinyl chloride-based resin,    or a mixture thereof.-   5. The active energy ray curable composition according to any one of    1 to 4 mentioned above, further including a multi-functional monomer    having at least two polymerizable unsaturated ethylene bonds    accounting for 15 percent by mass or less of the total amount of the    polymerizable compounds.-   6. The active energy ray curable composition according to any one of    1 to 5 mentioned above, further including an oligomer having a    polymerizable unsaturated ethylene bond accounting for 10 percent by    mass or less of the total amount of polymerizable compounds.-   7. The active energy ray curable composition according to any one of    1 to 6 mentioned above, wherein the active energy ray curable    composition is used for additive manufacturing.-   8. An active energy ray curable ink including the active energy ray    curable composition of any one of 1 to 7 mentioned above.-   9. The active energy ray curable ink according to 8 mentioned above,    wherein the active energy ray curable ink is used for inkjet.-   10. A composition stored container including the active energy ray    curable composition of any one of 1 to 7 mentioned above.-   11. A two dimensional or three dimensional image forming apparatus    including the container including the active energy ray curable    composition of any one of 1 to 7 mentioned above, and an irradiator    to emit an active energy ray.-   12. An image forming method including irradiating the active energy    ray curable composition of any one of 1 to 7 mentioned above with an    active energy ray.-   13. A cured material formed by curing the active energy ray curable    composition of any one of 1 to 7 mentioned above.-   14. A processed product manufactured by processing the cured    material of 13 mentioned above.

Having generally described preferred embodiments of this invention,further understanding can be obtained by reference to certain specificexamples which are provided herein for the purpose of illustration onlyand are not intended to be limiting. In the descriptions in thefollowing examples, the numbers represent weight ratios in parts, unlessotherwise specified.

EXAMPLES

Next, the present invention is described in detail with reference toExamples and Comparative Examples but not limited thereto.

Manufacturing of Non-polymerizable Resin

Resin A: Polyester-based Resin (Tg: 40 Degrees C.)

The following components were placed in a container equipped with acondenser, a stirrer and a nitrogen introducing tube to conduct reactionat 220 degrees C. for 5 hours while distilling away water produced in anitrogen atmosphere in such a manner that Tg became 40 degrees C.

-   -   Adduct of bisphenol A with 2 moles of propyleneoxide: 450 parts    -   Adduct of bisphenol A with 3 moles of propylene oxide: 280 parts    -   Terephthalic acid: 257 parts    -   Isophthalic acid: 65 parts    -   Maleic anhydride: 10 parts    -   Titanium dihydroxybis (triethanol aminate) as condensation        catalyst: 2 parts Thereafter, reaction is conducted under a        reduced pressure of from 5 mmHg to 20 mmHg followed by cooling        down to room temperature and pulverization to obtain Resin A.

Resin B: Epoxy Resin (Tg:10 Degrees C.)

The following recipe was charged into a separable flask equipped with astirrer, a thermometer, a nitrogen introducing tube, and a condenser:

-   -   Bisphenol A type epoxy resin (EPOMIC® RP140P, manufactured by        Mitsui Chemicals, Incorporated): 300 g    -   Bisphenol A: 97 g    -   Xylene: 50 mL

Thereafter, the system was heated in a nitrogen atmosphere and 1 mL of0.65 N sodium hydroxide was added. Thereafter, the system was heated toabout 150 degrees C. and in the middle xylene was distilled away under areduced pressure to conduct reaction at 180 degrees C. for five hours insuch a manner that Tg became 10 degrees C. to obtain Resin B.

The substrate and materials for use in Examples and Comparative Examplesare as follows.

Substrate

Polycarbonate film (PC)

-   -   Iupilon 100FE2000 (manufactured by Mitsubishi        Engineering-Plastics Corporation Masking, Thickness: 100 μm)

Material

Mono-functional Monomer

-   -   Tetrahydrofurfuryl acrylate: THFA (manufactured by OSAKA ORGANIC        CHEMICAL INDUSTRY LTD.)    -   Phenoxyethyl acrylate: PEA (manufactured by OSAKA ORGANIC        CHEMICAL INDUSTRY LTD.)    -   Isoboronyl acrylate: IBXA (manufactured by OSAKA ORGANIC        CHEMICAL INDUSTRY LTD.)    -   Cyclic trimethylol propane formal monoaacrylate: SR531        (manufactured by Sartomer Company)    -   2-methoxyethylacrylate: 2-MTA (manufactured by OSAKA ORGANIC        CHEMICAL INDUSTRY LTD.)    -   Isooctyl acrylate: IOA (manufactured by OSAKA ORGANIC CHEMICAL        INDUSTRY LTD.)    -   3,3,5-trimethylcyclohexane acrylate: CD420, manufactured by        Sartomer Company)    -   Cyclohexyl acrylate: CHA (manufactured by OSAKA ORGANIC CHEMICAL        INDUSTRY LTD.)

Non-polymerizable Resin

-   -   Resin A: Polyester-based Resin (Tg: 40 Degrees C.)    -   Resin B: Epoxy Resin (Tg: 10 Degrees C.)    -   VYLON: GA-1310 (Mn: 20×10³, manufactured by TOYOBO CO., LTD.)    -   VYLON: GA-443 (Mn: 18×10³, manufactured by TOYOBO CO., LTD.)    -   VYLON: GA-415 (Mn: 10×10³, manufactured by TOYOBO CO., LTD.)    -   VYLON: GA-1200 (Mn: 10×10³, manufactured by TOYOBO CO., LTD.)    -   VYLON: GA-920 (Mn: 30×10³, manufactured by TOYOBO CO., LTD.)        -   Elvacite 4026, Mw: 32,500 (manufactured by Lucite            International, Inc.)

Multi-functional Monomer

-   -   1,3-butylene glycol diacrylate: SR212 (manufactured by Sartomer        Company)    -   Trimethylol propane triacrylate (A-TMPT, manufactured by        Shin-Nakamura Chemical Co., Ltd.)

Oligomer

-   -   Polyester-based Urethane acrylate oligomer : Ultraviolet        UV-3010B (manufactured by The Nippon Synthetic Chemical Industry        Co., Ltd.)        -   Weight average molecular weight Mw: 9,690, Number of            saturated carbon-carbon bond=2.

Initiator

-   -   2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide : LUCIRIN TPO        (manufactured by BASF Japan)    -   1-hydroxy-cyclohexyl-phenyl-ketone : Irgacure 184 (manufactured        by BAFS Japan)    -   2,4-diethylthioxanthon : KAYACURE-DETX-S (manufactured by Nippon        Kayaku Co., Ltd.

Pigment

-   -   Carbon black

The mixing ratio of carbon black #10 (manufactured by MitsubishiChemical Corporation) to the polymer dispersant (S32000, manufactured byLubrizol Japan Ltd.) was 3:1 by mass.

In the present disclosure, Tg as a characteristics of themonomer-functional monomer represents the glass transition temperatureof a cured material of a homopolymer thereof. Tg in the catalog wasadopted first and if no catalog value exists, the Tg was measured by DSCmethod. Polymerization was conducted by a known solution polymerizationmethod.

-   -   A: toluene solution of 10 percent monomer    -   B: Initiator: Azobis isobutyl nitrile: 5 percent

After nitrogen purged, A and B were encapsulated.

Shaking for six hours while in hot bath at 60 degrees C.

The resultant was re-precipitated in a solvent in which the monomer wassoluble and the polymer was insoluble such as methanol or petroleumether followed by filtration to be taken out. The filtrated resultantwas used for DSC.

In this solution polymerization method, a polymer having a molecularweight from about several tens of thousands to hundreds of thousands wasobtained. In such a molecular weight range, the glass transitiontemperature is not thought to be dependent on the molecular weight sothat the glass transition temperature does not change depending onpolymerization conditions. The DSC instrument used was Seiko InstrumentsDSC120U. The range of the measuring temperature was from 30 degrees C.to 300 degrees C. and the temperature rising speed was 2.5 degrees C.per minute.

In the present disclosure, Tg as a characteristics of thenon-polymerizable resin was taken from the catalog and if no catalogvalue existed, the Tg was measured by DSC method. The DSC instrumentused was Seiko Instruments DSC120U. The range of the measuringtemperature was from 30 degrees C. to 300 degrees C. and the temperaturerising speed was 2.5 degrees C. per minute.

Example 1

The materials listed in Table 1 were sequentially added from the top tothe bottom of Table 1 while being stirred. After being stirred for onehour and confirmed the remaining of dissolution was few, the resultantwas filtered with a membrane filter to remove coarse particles which maycause head clogging to manufacture an ink. This ink was discharged ontoa polycarbonate film by an inkjet discharging device having GEN4 heads(manufactured by Ricoh Industry Company, Ltd.) to obtain a layer havinga thickness of 10 μm. Immediately after discharging, a curable materialwas obtained by irradiation of ultraviolet ray having a light amount of1,500 mJ/cm² by a UV irradiator (LH6, manufactured by Fusion SystemsJapan).

The figures of the monomer, the non-polymerizable resin, the pigment,and the initiator in Table 1 are represented in “parts by mass”.

Examples 2 to 23 and Comparative Examples 1 and 8

Inks were manufactured in the same manner as in Example 1 as shown inTables 1 and 2 followed by printing and curing to obtain a curedmaterial.

Each of the cured materials was measured about jetting characteristics,hardness, extensibility, bending processibility as described below. Theresults are shown in Tables 1 and 2.

Evaluation Method

Jetting (Discharging) Characteristics

As described above, the ink was discharged onto a polycarbonate film byan inkjet discharging device having GEN4 heads (manufactured by RicohIndustry Company, Ltd.) to obtain a layer having a thickness of 10 μm.The discharging conditions were:

-   Head temperature: 60 degrees C.-   Discharging voltage (piezo voltage): 7 V-   Drive frequency: 1    -   A: Droplets of jetting was discharged vertically without a        satellite droplet    -   B: Droplets contacted adjacent droplets or satellite droplets        observed

Hardness

Pencil hardness (before extension) was measured according to JISK5600-5-4 Scratch hardness (pencil method).

The core of a pencil having regulated dimensions, forms, and hardnesswere pressed against the ink applied surface and moved. The resultantmarks or other deficiencies are used to evaluate the resistance of theformed film. The deficiencies of the surface of the formed film causedby the core of a pencil includes the following: The deficiencies aredefined as follows:

-   (a): Plastic deformation: Dimple permanently formed on formed film    with causing no agglomeration destruction-   (b): Agglomeration destruction: scratches or destruction where the    material of the formed layer are removed are visually confirmed on    the surface.-   (c): Combination of (a) and (b): All the deficiencies may occur at    the final stage simultaneously.

The product or the application article to be tested were applied to aflat plate having a uniform surface with a uniform thickness. Afterdrying/reaction curing, the pencil hardness was measured by pressing apencil to a horizontal layer-formed surface while gradually increasingthe hardness thereof. The pencil was mounted in such a manner thatduring the test, the pencil was pressed to the surface with an angle of45 degrees and a load of 750 g. The hardness of the pencil was graduallyincreased until marks or spots were formed on the formed layer due tothe deficiencies described in (a), (b), and (c).

Device and Instrument

-   -   Pencil scratch hardness TQC WWW tester (specialized for load of        750 g) (manufactured by COTEC Corporation)    -   Pencil: Set of pencils (Mitsubishi UNI) made of wood for drawing        having the next hardness 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H,        3H, 4H, 5H, and 6H    -   Pencil sharpener: Special device that scrapes off only the wood        part of a pencil while leaving the cylinder-like core of the        pencil as was.    -   Polishing paper: 3M-P 1000

Sequence

Using a pencil sharpener, the wood portion of the sharpener is carefullyremoved in such a manner that the core of the pencil takes a smoothcylinder-like form free of scratches and 5 mm to 6 mm of the core isexposed.

Holding the pencil vertically, the core is made to contact the polishingpaper and move back and forth while keeping the angle of 90 degrees tomake the point of the core flat. This is continued until the cornerportion of the core has a smooth and circular cross section with nofragment or chipping. This is repeated every time a pencil is used.

The applied film is placed on a flat and solid horizontal surface. Thepencil is mounted at a position by a stopper where the testing device ishorizontal when the point of the pencil contacts an applied film.

Immediately after the point of the pencil is on the applied film, theinstrument is pushed away from the operator at least 7 mm at 0.5 mm/s to1 mm/s.

-   -   The applied film is visually checked to identify the level of        the marks defined in (a), (b), and (c).

At this point, if the powder of the core of the pencil of the appliedsurface is wiped off by a soft cloth or dry cotton and an inactivesolvent, this makes destruction evaluation easy. During this test, ithas to be careful to avoid an impact on the hardness of the testedportion.

When no mark is made, the test is repeated by increasing the hardnessscale until a mark having a length of 3 mm or longer occurs to the testportion while avoiding the test portion already pressed.

When a mark is made, the test is repeated by lowering the hardness scaleuntil no mark is made. The level of the deficiency is determinedaccording to the definition of (a), (b), and (c).

The hardness of the hardest pencil free of a mark is referred to aspencil hardness.

The test is made twice and if the two results are different one or morelevels apart from each other, the test is repeated.

Level Determination

-   -   A: Pencil hardness HB or higher    -   B: Pencil hardness B or 2B    -   C: Pencil hardness 2B or lower

Extensibility

Breaking elongation at 180 degrees C. was obtained by tension test andthe following relation:

-   -   Tension tester: AUTOGRAPH AGS-5kNX (manufactured by Shimadzu        Corporation)    -   Tension speed: 20 mm/min    -   Temperature: 180 degrees C.    -   Sample: JIS K6251 dumbbell-like form (No. 6)        (Length after tension test−length before tension test)/(Length        before tension test)×100        Level Determination    -   A: 100% or more    -   B: 50 percent or more to less than 100 percent    -   C: Less than 50 percent

Bending Property

A cured material manufactured in the conditions described above was cutto 10 mm×50 mm and folded and bent by a bending tester having a coremandrel of 2 mm. The bending property was evaluated by crackingoccurring to the cured material.

Level Determination

-   -   A: Nothing wrong (no cracking)    -   B: one or two cracking    -   C: three to ten cracking    -   D: ten or more thin cracking    -   E: ten or more thick cracking

TABLE 1 Tg Example Example Example Example (degrees C.) 1 2 3 4 MixingMonomer Mono- THFA −12 100 100 functional PEA −22 IBXA 97 100 SR531 32100 2-MTA −50 IOA −58 CD420 29 CHA 15 Multi- SR-212 Bi- functionalfunctional A-TMPT Tri- functional Oligomer UV3010B Non- Resin A 40 1.2polymerizable Resin B 10 resin GA-1310 27 1.2 GA-443 14 1.2 GA-415 −8GA-1200 0 GM-920 −60 Elvacite 4026 75 1.2 Initiator LUCIRIN TPO — 5 5 55 Irgacure 184 — 7.5 7.5 7.5 7.5 DETX 2 2 2 2 Pigment Carbon Black —Evaluation Jetting — A A A A Characteristics |Tgp − Tgm} degrees C. — 5743 39 26 Hardness — — A A A A Extensibility — — A A A A Bending B C A Aproperty Tg Example Example Example Example (degrees C.) 5 6 7 8 MixingMonomer Mono- THFA −12 functional PEA −22 100 IBXA 97 100 100 SR531 3250 2-MTA −50 50 IOA −58 CD420 29 CHA 15 Multi- SR-212 Bi- functionalfunctional A-TMPT Tri- functional Oligomer UV3010B Non- Resin A 40polymerizable Resin B 10 1.2 resin GA-1310 27 1.2 GA-443 14 GA-415 −8 2GA-1200 0 2 GM-920 −60 Elvacite 4026 75 Initiator LUCIRIN TPO — 5 5 5 5Irgacure 184 — 7.5 7.5 7.5 7.5 DETX 2 2 2 2 Pigment Carbon Black —Evaluation Jetting — A A A A Characteristics |Tgp − Tgm} degrees C. —105 97 49 19 Hardness — — A A A A Extensibility — — A A A A Bending A AA A property Tg Example Example Example Example (degrees C.) 9 10 11 12Mixing Monomer Mono- THFA −12 100 functional PEA −22 85 85 85 IBXA 97SR531 32 2-MTA −50 IOA −58 CD420 29 CHA 15 Multi- SR-212 Bi- 15 5functional functional A-TMPT Tri- 5 functional Oligomer UV3010B 10 10Non- Resin A 40 polymerizable Resin B 10 resin GA-1310 27 0.6 GA-443 140.6 1.2 1.2 1.2 GA-415 −8 GA-1200 0 GM-920 −60 Elvacite 4026 75Initiator LUCIRIN TPO — 5 5 5 5 Irgacure 184 — 7.5 7.5 7.5 7.5 DETX 2 22 2 Pigment Carbon Black — Evaluation Jetting — A A A A Characteristics|Tgp − Tgm} degrees C. — 33 36 36 36 Hardness — — A A A A Extensibility— — A A A B Bending A A A A property Tg Example Example Example Example(degrees C.) 13 14 15 16 Mixing Monomer Mono- THFA −12 50 100 functionalPEA −22 50 80 80 IBXA 97 SR531 32 2-MTA −50 IOA −58 CD420 29 CHA 15Multi- SR-212 Bi- 20 5 functional functional A-TMPT Tri- functionalOligomer UV3010B 15 Non- Resin A 40 polymerizable Resin B 10 resinGA-1310 27 GA-443 14 1.2 1.2 1.2 1.2 GA-415 −8 GA-1200 0 GM-920 −60Elvacite 4026 75 Initiator LUCIRIN TPO — 5 5 5 5 Irgacure 184 — 7.5 7.57.5 7.5 DETX 2 2 2 2 Pigment Carbon Black — 5 Evaluation Jetting — A A AA Characteristics |Tgp − Tgm} degrees C. — 31 26 36 36 Hardness — — A AA B Extensibility — — A A B B Bending A A B A property Tg ExampleExample Example Example (degrees C.) 17 18 19 20 Mixing Monomer Mono-THFA −12 functional PEA −22 IBXA 97 100 SR531 32 2-MTA −50 IOA −58 100CD420 29 100 CHA 15 100 Multi- SR-212 Bi- functional functional A-TMPTTri- functional Oligomer UV3010B Non- Resin A 40 polymerizable Resin B10 resin GA-1310 27 GA-443 14 1.2 1.2 GA-415 −8 GA-1200 0 2 GM-920 −60Elvacite 4026 75 2.5 Initiator LUCIRIN TPO — 5 5 5 5 Irgacure 184 — 7.57.5 7.5 7.5 DETX 2 2 2 2 Pigment Carbon Black — Evaluation Jetting — A AA A Characteristics |Tgp − Tgm} degrees C. — 83 60 72 29 Hardness — — AA A A Extensibility — — A A A A Bending A A A A property Tg ExampleExample Example (degrees C.) 21 22 23 Mixing Monomer Mono- THFA −12functional PEA −22 IBXA 97 100 SR531 32 2-MTA −50 IOA −58 100 CD420 29100 CHA 15 Multi- SR-212 Bi- functional functional A-TMPT Tri-functional Oligomer UV3010B Non- Resin A 40 polymerizable Resin B 10resin GA-1310 27 GA-443 14 GA-415 −8 GA-1200 0 GM-920 −60 2 2 Elvacite4026 75 2.5 Initiator LUCIRIN TPO — 5 5 5 Irgacure 184 — 7.5 7.5 7.5DETX 2 2 2 Pigment Carbon Black — Evaluation Jetting — A A ACharacteristics |Tgp − Tgm| degrees C. — 133 89 157 Hardness — — A A AExtensibility — — A A A Bending A A A property

TABLE 2 Tg Comparative Comparative Comparative (degrees C.) Example 1Example 2 Example 3 Mixing Monomer Mono- THFA −12 100 functional PEA −22100 IBXA 97 100 SR531 32 2-MTA −50 IOA −58 CD420 29 CHA 15 Multi- SR-212Bi- functional functional A-TMPT Tri- functional Oligomer UV3010B Non-Resin A 40 polymerizable Resin B 10 resin GA-1310 27 GA-443 14 GA-415 −82 GA-1200 0 2 GM-920 −60 Elvacite 4026 75 2.5 Initiator DAROCURE TPO — 55 5 Irgacure 184 — 7.5 7.5 7.5 DETX — 2 2 2 Pigment Carbon Black —Evaluation Jetting — A A A Characteristics |Tgp − Tgm| degrees C. — 4 2222 Hardness — — A C A Extensibility — — A A A Bending — — D B D propertyTg Comparative Comparative Comparative (degrees C.) Example 4 Example 5Example 6 Mixing Monomer Mono- THFA −12 100 functional PEA −22 IBXA 97SR531 32 2-MTA −50 IOA −58 100 CD420 29 CHA 15 100 Multi- SR-212 Bi-functional functional A-TMPT Tri- functional Oligomer UV3010B Non- ResinA 40 polymerizable Resin B 10 resin GA-1310 27 GA-443 14 1.2 GA-415 −8GA-1200 0 2 GM-920 −60 2 Elvacite 4026 75 Initiator DAROCURE TPO — 5 5 5Irgacure 184 — 7.5 7.5 7.5 DETX — 2 2 2 Pigment Carbon Black —Evaluation Jetting — A A A Characteristics |Tgp − Tgm| degrees C. — 1 4858 Hardness — — C C C Extensibility — — A A A Bending — — E B B propertyTg Comparative Comparative (degrees C.) Example 7 Example 8 MixingMonomer Mono- THFA −12 functional PEA −22 IBXA 97 SR531 32 2-MTA −50 IOA−58 CD420 29 100 CHA 15 Multi- SR-212 Bi- 90 functional functionalA-TMPT Tri- functional Oligomer UV3010B 10 Non- Resin A 40 polymerizableResin B 10 resin GA-1310 27 GA-443 14 1.2 GA-415 −8 2 GA-1200 0 GM-920−60 Elvacite 4026 75 Initiator DAROCURE TPO — 5 5 Irgacure 184 — 7.5 7.5DETX — 2 2 Pigment Carbon Black — Evaluation Jetting — A ACharacteristics |Tgp − Tgm| degrees C. — — 15 Hardness — — A AExtensibility — — C A Bending — — E D property

As seen in the results of Examples 1 to 23, when the absolute value ofthe difference between the glass transition temperature Tg_(p) of thenon-polymerizable resin and the glass transition temperature Tg_(m) of ahomopolymer of the mono-functional monomer having a single polymerizableunsaturated ethylene double bond is 19 degrees C. or higher, Tg_(H)≧10degrees C., where Tg_(H) represents the higher of Tg_(p) and Tg_(m), andTg_(L)≦40 degrees C., where Tg_(L) represents the lower of Tg_(p) andTg_(m), it is possible to strike a balance among hardness,extensibility, and bending property of the cured material.

According to the present invention, an active energy ray curablecomposition is provided by which a cured material is obtained striking abalance between high hardness and extensibility while maintainingbending property.

Having now fully described embodiments of the present invention, it willbe apparent to one of ordinary skill in the art that many changes andmodifications can be made thereto without departing from the spirit andscope of embodiments of the invention as set forth herein.

What is claimed is:
 1. An active energy ray curable compositioncomprising: a non-polymerizable resin; and polymerizable compoundscomprising a mono-functional monomer having a single polymerizableunsaturated ethylene double bond, wherein the following relations aresatisfied:ΔTg=|Tg _(p) −Tg _(m)|≧20 degrees C., where Tg_(p) represents a glasstransition temperature of the non-polymerizable resin and Tg_(m)represents a glass transition temperature of a homopolymer of themono-functional monomer,Tg_(H)≧20 degrees C., where Tg_(H) represents the higher of Tg_(p) andTg_(m), andTg_(L)≦0 degrees C., where Tg_(L) represents the lower of Tg_(p) andTg_(m).
 2. The active energy ray curable composition according to claim1, wherein the non-polymerizable resin is selected from the groupconsisting of an acylic-based resin, an epoxy-based resin, aketone-based resin, a nitrocellulose-based resin, a phenoxy-based resin,a polyester-based resin, a polyurethane-based resin, a polyvinylchloride-based resin, and a mixture thereof.
 3. The active energy raycurable composition according to claim 1, further comprising amulti-functional monomer having at least two polymerizable unsaturatedethylene bonds accounting for 15 percent by mass or less of a totalamount of the polymerizable compounds.
 4. The active energy ray curablecomposition according to claim 1, further comprising an oligomer havinga polymerizable unsaturated ethylene bond accounting for 10 percent bymass or less of a total amount of polymerizable compounds.
 5. The activeenergy ray curable composition according to claim 1, wherein the activeenergy ray curable composition is used for additive manufacturing.
 6. Anactive energy ray curable ink comprising: the active energy ray curablecomposition of claim
 1. 7. The active energy ray curable ink accordingto claim 6, wherein the active energy ray curable ink is used forinkjet.
 8. A composition stored container comprising: the active energyray curable composition of claim
 1. 9. A two dimensional or threedimensional image forming apparatus comprising: a storing partcomprising the active energy ray curable composition of claim 1; and anirradiator to emit an active energy ray.
 10. An image forming methodcomprising: irradiating the active energy ray curable composition ofclaim 1 with an active energy ray.
 11. A cured material formed by curingthe active energy ray curable composition of claim
 1. 12. A processedproduct formed by processing the cured material of claim
 11. 13. Theactive energy ray curable composition according to claim 1, wherein themono-functional monomer is at least one selected from the groupconsisting of phenoxyethyl acrylate, tetrahydrofurfuryl acrylate,isobornyl acrylate, cyclic trimethyl propane formal monoacrylate,2-methoxyethyl acrylate, isooctyl acrylate, 3,3,5-trimethylcyclohexaneacrylate, and cyclohexyl acrylate.
 14. The active energy ray curablecomposition according to claim 1, wherein the mono-functional monomer isat least one selected from the group consisting of tetrahydrofurfurylacrylate, isobornyl acrylate, cyclic trimethyl propane formalmonoacrylate, 2-methoxyethyl acrylate, isooctyl acrylate,3,3,5-trimethylcyclohexane acrylate, and cyclohexyl acrylate.
 15. Anactive energy ray curable composition comprising: a non-polymerizableresin; and polymerizable compounds comprising a mono-functional monomerhaving a single polymerizable unsaturated ethylene double bond, whereinthe following relations are satisfied:ΔTg =|Tg _(p) −Tg _(m)|≧19 degrees C., where Tg_(p) represents a glasstransition temperature of the non-polymerizable resin and Tg_(m)represents a glass transition temperature of a homopolymer of themono-functional monomer,Tg_(H) ≧10 degrees C., where Tg_(H) represents the higher of Tg_(p) andTg_(m), andTg_(L) ≦40 degrees C., where Tg_(L) represents the lower of Tg_(p) andTg_(m), wherein the mono-functional monomer is at least one selectedfrom the group consisting of tetrahydrofurfuryl acrylate, isobornylacrylate, cyclic trimethyl propane formal monoacrylate, 2-methoxvethylacrylate, isooctyl acrylate, 3,3,5-trimethylcyclohexane acrylate, andcyclohexyl acrylate.
 16. The active energy ray curable compositionaccording to claim 15, wherein the following relations are satisfied:Tg_(H)≧14 degrees C., where Tg_(H) represents the higher of Tg_(p) andTg_(m), andTg_(L)≦20 degrees C., where Tg_(L)represents the lower of Tg_(p) andTg_(m).
 17. The active energy ray curable composition according to claim15, wherein the following relations are satisfied:Tg_(p)≧10 degrees C., andTg_(m)≦40 degrees.